Perylene Dyes with High Resistance to Alkali

Langhals, Heinz; Jaschke, Harald; Bastani-Oskoui, Haleh; Speckbacher, Markus

doi:10.1002/ejoc.200500129

Cited by 13 publications

(14 citation statements)

References 20 publications

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“…However, synthesis under selected conditions and subsequent recrystallisation would result in pure colourless materials. Alkyl substituents with hydroxy groups in position 3 cause special dense packings in perylene dyes and protect the tetracarboxdiimide groups against hydrolysis 8. Thus, we introduced such substituents into the naphthalene‐tetracarboxdiimides starting with cyanoacetate according to Scheme , subsequent alkylation, reduction to the amino alcohol and condensation with naphthalene‐1,8:4,5‐tetracarboxylic dianhydride.…”

Section: Resultsmentioning

confidence: 99%

“…and 25 % sodium methoxide solution in methanol (91 mL, 400 mmol, 2 equiv.) were allowed to react according to ref 8…”

Section: Methodsmentioning

confidence: 99%

“…and LiAlH 4 (5.92 g, 156 mmol, 1.3 equiv.) were allowed to react according to ref 8. and purified by kugelrohr distillation in medium vacuum.…”

Section: Methodsmentioning

confidence: 99%

“…2,7‐Bis[2‐ethyl‐2‐(hydroxymethyl)butyl]benzo[ lmn ][3,8]phenanthroline‐1,3,6,8(2 H ,7 H )‐tetraone (1a): Isochromeno[6,5,4‐ def ]isochromene‐1,6,8‐tetraone (410 mg, 1.53 mmol) and 2‐(aminomethyl)‐2‐ethylbutan‐1‐ol8 (600 mg, 4.60 mmol, 3 equiv.) in DMF (25 mL) were refluxed (bath 110 °C) for 2 h (colour change to red), cooled and further cooled with ice, quenched by the cautious addition of 2 n HCl (50 mL), collected by vacuum filtration, washed with a small amount of distilled water, dried in air at 110 °C, suspended in a small amount of methanol, refluxed with 10 % K 2 CO 3 , collected by vacuum filtration, washed with a mixture of methanol/dist.…”

Section: Methodsmentioning

confidence: 99%

“…2,7‐Bis[2‐butyl‐2‐(hydroxymethyl)hexyl]benzo[ lmn ][3,8]phenanthroline‐1,3,6,8(2 H ,7 H )‐tetraone (1c): Isochromeno[6,5,4‐ def ]isochromene‐1,3,6,8‐tetraone (1.31 g, 4.89 mmol), 2‐(aminomethyl)‐2‐butylhexan‐1‐ol8 (2.75 g, 14.7 mmol) and DMF (70 mL) were allowed to react analogously to 1a . Yield 985 mg (1.62 mmol, 33 %) pale pink, shiny solid; a colourless solid was obtained after several recrystalliations from chloroform, m.p.…”

Section: Methodsmentioning

confidence: 99%

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γ‐(Hydroxyalkyl)naphthalene‐tetracarboxdiimides: Organic White Pigments

Langhals

Ritter

2008

Eur J Org Chem

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Section: Resultsmentioning

confidence: 99%

“…and 25 % sodium methoxide solution in methanol (91 mL, 400 mmol, 2 equiv.) were allowed to react according to ref 8…”

Section: Methodsmentioning

confidence: 99%

“…and LiAlH 4 (5.92 g, 156 mmol, 1.3 equiv.) were allowed to react according to ref 8. and purified by kugelrohr distillation in medium vacuum.…”

Section: Methodsmentioning

confidence: 99%

Section: Methodsmentioning

confidence: 99%

Section: Methodsmentioning

confidence: 99%

See 3 more Smart Citations

γ‐(Hydroxyalkyl)naphthalene‐tetracarboxdiimides: Organic White Pigments

Langhals

Ritter

2008

Eur J Org Chem

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Perylenbisimid‐Dimere als fluoreszenter “Klebstoff” für DNA und zum Nachweis von Basenfehlpaarungen

Baumstark

Wagenknecht

2008

Angewandte Chemie

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Perylen-3,4:9,10-tetracarbonsäurebisimid (PB) und dessen Derivate werden aufgrund ihrer hervorragenden photochemischen Stabilität und der hohen Quantenausbeuten gerne als Fluoreszenzfarbstoffe in organischen Materialien eingesetzt. [1,2] Die starken hydrophoben Wechselwirkungen zwischen den einzelnen PB-Chromophoren machen diesen Farbstoff zu einem wichtigen Baustein für funktionelle supramolekulare Architekturen. [1,3] Betrachtet man die Kombination dieser Eigenschaften, erscheint es interessant, PB in der dimeren Form auch als Sonde für die fluoreszente DNAund RNA-Analytik einzusetzen. Die nicht-kovalente Bindung an DNA wurde mit PB-Derivaten untersucht, die mit Spermin [4] oder anderen Aminen modifiziert wurden.[5] Darüber hinaus erschien in den letzten Jahren eine zunehmende Zahl von Publikationen, die die kovalente Modifikation von Oligonucleotiden mit PB beschreiben. [6][7][8][9][10][11][12] Kürzlich stellten wir eine einfache Syntheseroute für den Einbau von PB als artifizielle DNA-Base vor, um die Stapelungseigenschaften dieses Farbstoffes an spezifischen Stellen in Doppelstrang-DNA untersuchen zu können.[13] Hier präsentieren wir nun die Evaluierung der optischen Funktionalisierung mit PBDimeren anhand dreier exemplarischer Doppelstränge (DNA1, DNA3 und DNA4 a). Für die synthetische Modifizierung der entsprechenden Oligonucleotide mit dem PBChromophor (Schema 1) wurde der 2-Desoxyribofuranosidteil durch ein acyclisches Linkersystem ersetzt, das über eines der beiden Imid-Stickstoffatome des PB-Farbstoffes angeknüpft wurde.[13] Dieser Linker ermöglicht es dem Chromophor, in den Basenstapel zu interkalieren, und er weist die für die automatisierte Phosphoramiditchemie erforderliche hohe chemische Stabilität auf. [13,14] DNA1 enthält ein Interstrang-PB-Dimer, wohingegen DNA3 je ein PB-Monomer außerhalb des Doppelstrangs an beiden 5'-Enden trägt. Beide Doppelstränge weisen palindromische Sequenzen auf. Die Fluoreszenzspektren beider Doppelstränge DNA1 und DNA3 (Anregung bei 505 nm) werden von einer breiten Bande bei 660 nm ohne Feinstruktur dominiert (Abbildung 1). Diese excimerartige Emission des PB-Dimers wurde auch in Nanoaggregaten von Perylenbismiden beobachtet. [3,8,15] Die UV/Vis-Spektren von DNA1 und DNA3 (Abbildung 2) zeigen bei niedriger Temperatur zwei Hauptbanden, die im Vergleich zu den vibronischen Übergängen (0!1 und 0!0) des PB-Monomers hypsochrom (506 nm) bzw. bathochrom (545 nm) verschoben sind.[16]Dieses Resultat belegt die starken excitonischen p-p-Wechselwirkungen zwischen den beiden PB-Chromophoren im Inneren des Doppelstrangs (DNA1) bzw. außen am Doppelstrang (DNA3).[15]Sowohl die excimerartige Fluoreszenzbande als auch die verschobenen Absorptionsbanden von DNA1 verschwinden bei höheren Temperaturen. Besonders bemerkenswert ist Schema 1. PB-modifizierte Doppelstränge DNA1-DNA3, DNA4 a-DNA4 e. Abbildung 1. Temperaturabhängige Fluoreszenzspektren von DNA1 (oben) und DNA3 (unten), 1.25 mm DNA-Doppelstrang, 10 mm Na-P iPuffer, 250 mm NaCl, pH 7, Anregung bei 505 nm.

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Perylene Bisimide Dimers as Fluorescent “Glue” for DNA and for Base‐Mismatch Detection

2008

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Perylene-3,4:9,10-tetracarboxylic acid bisimide ("PB") and its derivatives are applied as fluorescent dyes in organic materials owing to their excellent photochemical stability as well as the high fluorescence quantum yields. [1,2] The strong hydrophobic stacking interactions between the PB chromophores make this dye an important building block for functional supramolecular architectures. [1,3] Based on these properties, PB in the dimeric form should be also of potential interest as a probe for fluorescent DNA/RNA analytics as well as for functionalized DNA-based architectures. Its noncovalent DNA-binding interactions have been studied with PB derivatives that had been modified with spermine [4] or other amines.[5] Moreover, an increasing number of publications about covalent modifications of oligonucleotides with PB have appeared over the last few years. [6][7][8][9][10][11][12] Recently, we presented a facile route for the synthetic incorporation of PB as an artificial DNA base in order to study the stacking interactions of this dye at specific sites in duplex DNA.[13]Herein, we present the evaluation of fluorescent PB dimers for the optical functionalization of DNA using three representative duplexes (DNA1, DNA3, and DNA4 a). For the synthetic modification of the corresponding oligonucleotides with the PB chromophore (Scheme 1), the 2-deoxyribofuranoside moiety was replaced by an acyclic linker system which is tethered to one of the imide nitrogens of the PB dye.[13] This linker allows the chromophore to intercalate in the base stack while providing high chemical stability during the automated phosphoramidite chemistry. [13,14] DNA1 bears one interstrand PB dimer inside the duplex, whereas DNA3 contains a PB monomer outside the duplex at each 5' end. Both duplexes contain palindromic sequences. When DNA1 and DNA3 are excited at 505 nm, the fluorescence spectra of both duplexes (Figure 1) are dominated by a broad band at % 660 nm without fine structure. This band corresponds to the excimer-type emission of the PB dimer that has been observed in nanoaggregates of perylene bisimides. [3,8,15] The UV/Vis spectra of DNA1 and DNA3 (Figure 2) at low temperatures show two major bands that are hyposochromically (506 nm) or bathochromically (545 nm) shifted in comparison to the 0!1 and 0!0 vibronic transitions of the PB monomer.[16] This result shows the strong p-p excitonic interactions of the two PB chromophores inside (DNA1) and outside (DNA3) of the duplex. [15] Both the excimer-type fluorescence band and the shifted absorption bands of DNA1 vanish at higher temperatures. It is remarkable that this occurs cooperatively at a temperature (75.9 8C) that corresponds to the cooperative thermal dehybridization of the whole DNA duplex, which is typically measured at 260 nm (T m = 78.6 8C). Apparently the intact helical duplex is required as a framework for the PB dimer formation. In comparison to the unmodified DNA2 (T m = 76.2 8C) the duplex DNA1 is stabilized by 2.4 8C through the Scheme 1. PB-modified duplexes DNA1-DNA3...

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Perylene Dyes with High Resistance to Alkali

Cited by 13 publications

References 20 publications

γ‐(Hydroxyalkyl)naphthalene‐tetracarboxdiimides: Organic White Pigments

γ‐(Hydroxyalkyl)naphthalene‐tetracarboxdiimides: Organic White Pigments

Perylenbisimid‐Dimere als fluoreszenter “Klebstoff” für DNA und zum Nachweis von Basenfehlpaarungen

Perylene Bisimide Dimers as Fluorescent “Glue” for DNA and for Base‐Mismatch Detection

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